Photographic silver halide light-sensitive element



Unite States Patent C) US. Cl. 96104 18 Claims ABSTRACT OF THE DISCLOSURE A photographic silver halide element comprising a support and a light-sensitive emulsion containing the sensitizing dye having the general formula:

wherein R represents a member selected from the group consisting of the following class A and the following class B.

Class A:

and

CH2CHCH'JSO3H GOCH,

3,511,664 Patented May 12, 1970 range of the light sensitive wave length of the silver halide emulsion is enlarged and the emulsion is optically sensitized. Moreover, it has also been known that among various sensitizing dyes, a rhodacyanine sensitizing dye provides a photographic silver halide emulsion with a red sensitivity.

The rhodacyanine sensitizing dyes having the general Formula I sensitize remarkably a silver halide emulsion;

I ia (I) wherein R represents a group selected from class A and class B, R represents a group selected from class B, and R represents a group selected from class A.

Class A:

(CHzCHzOhSOaH, CH2OHCH2OSO3H, CHzCHCHzSOaH GHzOHzSOaH, CHzCHzCHzSOaH, CHzCHzCHzCHzSOgH CHg(|3HCHzO(CH2)3SO H, CHzCHCHzOCH:

Class B: an alkyl group having less than 6 carbon atoms and allyl group (wherein, if R is selected from class A, SO H of the group may be in the state of its salt); and Y represents a non-metal atom necessary of forming a heterocyclic ring consisting of thiazoles and benzoxazoles.

Besides providing a silver halide emulsion with a high sensitivity, the sensitizing dye having above-mentioned general Formula I has such merits that in case where the sensitizing dye is present together with a water-soluble or oil-soluble coupler in an emulsion before coating, the reduction of the coupler in sensitivity is extremely less and hence a highly sensitive emulsion is obtained as compared with the case of using a sensitizing dye wherein R and R are alkyl groups, aralkyl groups, or alkenyl groups. Further, as the general characteristics peculiar to the rhodacyanine dye having a quinoline ring at the wherein R and R each represents a member selected from the group consisting of a halogen atom, a hydroxyl group, and NHR R represents a member selected from the group consisting of an aryl group and aralkyl group; and R represents a member selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, and an amine salt.

position as shown in general Formula I, the light sensitive element prepared by employing such a sensitizing dye has an excellent range and position of spectral sensitive wave length suitable for the red-sensitive layer material of a multi-layer color photographic light-sensitive element. However, there is a fault that a silver halide light-sensitive element containing the sensitizing dye (I) tends to reduce its sensitivity during preservation. Accordingly, in spite of the excellent properties of the sensitizing dye (I), such a dye alone has not been practically used.

However, the above-mentioned sensitizing dye (I) may be used in some condition, that is, there is an example where such a dye is employed together with some kind of water-soluble coupler since such a coupler is considered to have a function of correcting the above-mentioned faults of the sensitizing dye.

3 4 .Therefore, an object of this invention is to enable the B in formula (HI) are a triazinyl group is illustrated by practical use of the rhodacyanine dye shown by general the general Formula IV.

Formula I in photography.

Other objects of the present invention is to provide a protographic silver halide light-sensitive element contain- N N ing the rhodacyanine dye having general Formula I With- -f T -N W R1 out accompanied with the above-mentioned fault. I

Other objects and the merits of the present invention V V will become apparent from the following description of our invention. 10 R10 8 These objects are accomplished according to the instant (1v) invention by incorporating in the silver halide emulsion layer containing the rhodacyanine sensitizing dye having I general Formula I the compound having the general The extent of the supersensitizing effect by the above Formula II compound is varied according to the kinds of groups R N N NH-W lNn--on=on NH Y I I N \//N son) son) Kl R4 R wherein R and R each represents a halogen atom, a R R and R That is, among the compounds having hydroxyl group or NHR (where, R is an aryl group the above Formula IV, the compound having or an aralkyl group) and D is a hydrogen atom, an alkali metal, ammonium, or an amine salt. 5 NH/\ The inventors have found that by incorporating the I compound (II) the reduction in sensitivity of the photographic silver halide light-sensitive element containing the sensitizing dye (1) during preservation can be markas R and R corresponds to compound (II) of our inedly prevented. vention, and the combination of only the compound That it has been found that the sensitizing y (II) and sensitizing dye (I) has the effect of preventing the Pl'aetleel use of Which alone is considered to be dllllsensitivity reduction during preservation, which is a feacult in spite of the above-mentioned many merits can be t of our invention. Compound (II) of our invention heed Practically y incorporating ill a Silver halide ehllllhas never been noticed from a view point of supersensi- SlOIl the sensitizing y together Wlth the Cempollnd tization, and it has never been attempted to incorporate in aeeordehee With the Present invention, whereby in a silver halide emulsion the compound (II) together the sensitizing dye can be eifectively utilized without givith a iti i d F h a i il case to th ing bad influences on the preservability. above-cited Japanese patent is disclosed in U.S. Pat. The present invention Will now be cXpl While 2,947,630 wherein a supersensitizing elfect is obtained by comparing With conventional known fl P 40 using a rhodacyanine sensitizing dye and a compound For example, there is disclosed in Japanese P t similar to compound (II) of our invention, but as men- 53 that a supefsehsltlzlhg efieet can he Obtained y tioned above in connection with the Japanese patent, the us g t compound having the following general purpose and the effect of the U.S. patent are different mula HI similar to the above- Compound from those of our invention, which can be attained by used in our invention to a sensitizing dye. using only the specific compound and the specific sensi- The known compound has the general formula tizing dye.

That is, as shown in below Example 3, there are com- B pounds having an effect of preventing the sensitivity re- Q duction of light sensitive elements during preservation X (H1) and compounds showing no suchaction although they have a slmilar structure and a similar super color sensi- Wherein B and B each represents tizing power, and among the compounds (I11) and the compounds similar to them, only compounds (II) have f- SR a power of preventing the reduction in sensitivity of the light-sensitive element during preservation.

It is also disclosed in British Pat. 852,074 that a compound similar to the compound (II) has a antifoggant and/or antistain action in a photographic emulsion con- (where R and R each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an acyl p, all y y p, a Substituted unsubstituted taining a coupler. However, the reduction in sensitivity ealhamyl group, a heteroeyelle g p a group havlllg of a light sensitive element containing the sensitizing a heteloeyelle ring) and X and each represents a dye (I) during preservation occurs independently of the drogen atom 01' H- presence of coupler and the prevention of the reduction n the above-Cited P there is I10 lllllltatloll about in sensitivity according to the present invention can be the SellSltlZhlg y and also the Scope of compound accomplished independently of the presence of coupler. is very large. However, the supersensitizing effect by the r Th known compounds d ib i the b addition of compound (III) has no relation to the effect 69 tioned British patent are mainly aminostilbene compounds for preventing the reduction of sensitivity by the addition b t i h uld b n i ed that th compound (II used in of compound (II), and the sensitivity-re i n prcv ntthe present invention is weak soluble in water while watering elfect by the addition of compound in accordance soluble aminostilbene compounds cannot prevent the re- With the present invention can be obtained about only duction in sensitivity of light-sensitive elements during the sensitizing dye shown by general Formula I, that is, 70 preservation. Further, an aminostilbene compound has the addition of compound (II) is ineffective in the case been known as a fluorescent whitening agent and when of using other sensitizing dyes. it is used in photographic light-sensitive elements, in par- For example, among the compounds shown by genticular, it is used in a large proportion, the reflection deneral Formula III, ones most similar to the compound (II) sity (maximum density) of an image of the photographic of our invention, that is, the compound wherein B and light sensitive element after processing is reduced by the weak-soluble compound (II) of the present invention since the fluorescence thereof in the image layer is very weak.

Listed below are representative compounds selected from those represented by Formula I, although our invention is not limited in any sense to these particular compounds.

Ho N CH CH c s S as t=GH C I N N C2H5 pound (II) may be added in a silver halide emulsion as a solution of an organic solvent such as methanol and ethanol. The addition of the sensitizing dye (I) and H H H H N H Hm N 1 J N n N H H i. H N nm N PH m m M. m M

M m w m H H E H m n m d me C a C N. O a

a m H Mb 0 0 o t S S S ev H H H oi H N HH ll 1 YQ r oo Nr 1 mm IN 1N md H H H E N N N mus saw) I mmm m H fa a a N r n H N 0 N Q H i O s a "n w H m 0 S H N N V H N 0 J H N A suitable density of the sensitizing dye (I) of this inthe compound (II) is conducted prior to coating. The vention in a silver halide emulsion is 0.002 to 0.2 g. sensitizing dye (I) may be added in a silver halide emulper mol of silver halide and that of the compound (II) 70 sion before or after or together with the compound (II). is 0.05 to 1 g. per mol of silver halide, and the ratio of For the silver halide emulsion in this invention may the sensitizing dye (I) to compound (II) is suitably from be used various silver salts, such as, silver chloride, 1:2 to 1:200, in particular from 1:10 to 1:60. silver bromide, silver iodide, silver iodo-bromide, silver The sensitizing dye (I) may be added in a silver halide chloro-bromide or silver chloro-iodo-bromide and also emulsion in a manner well known 1n the field The com- 75 the silver halide emulsion may contain such usual additives as, a chemical sensitizer, a hardening agent, an antifoggant, a wetting agent, a stabilizer, a plasticizer, a developing accelerator, and a anti-bronzing agent as well as a coupler capable of forming a cyan image by color development.

The silver halide emulsion may be applied by a suitable manner to a suitable support such as a glass plate,

a film of a cellulose derivative, a film of a synthetic resin or a baryta paper.

The following are examples of the present invention.

EXAMPLE 1 A silver chloro-bromide emulsion (chloridezbromide=60 moles:40 moles) containing the sensitizing dye (I) was applied to a film base of cellulose acetate. Apart from this, the same silver halide emulsion containing the sensitizing dye (I) together with the compound (H) was applied to a film base of cellulose acetate. Thus prepared light sensitive films were measured about the sensitivities directly after coating and after preserved for a long period of time and the change of the sensitivities are shown in Table 2.

The sensitivity was shown by the red sensitivity obtained by exposing through Fuji-7 Filter (transmitting the light having longer wave lengths than 590 millimicrons. The sample was preserved for 180 days at a temperature of 23 C. and at a relative humidity of 60%. The development was conducted for 6 minutes using the developer showing in Table 1. The sensitivity value was Shown by log E (where E is the exposure amount necessary for providing fog+optical density being 0.1). The sensitivity change by preservation (A log E) was shown by a value of log E directly after coating subtracted by the value of log E after preservation.

From the results shown in Table 2, it is clear that the change insensitivity of the light-sensitive element after SO Na preservation is remarkably reduced by incorporating the compound (II) together with the sensitizing dye (I).

10 EXAMPLE 2 CONH(CH2)13CH;

was applied to a baryta paper. Apart from this, a photographic emulsion containing the sensitizing dye (I), the

coupler dispersion same as above, and the compound (H) was applied to a baryta paper similarly.

The sensitivity change of the both types of thus prepared light-sensitive papers was measured between the ones directly after coating and ones after preservation, the results of which are shown in Table 4.

The filter for exposure and the preservative conditions were same as in Example 1. The development was conducted for 9 minutes at 20 C. in the developer shown in Table 3. Thus developed photographic paper was, rinsed with water, fixed, bleached, and then rinsed with water. The sensitivity value was indicated by log E (E is an exposure amount necessary for giving fog+optical density being 0.1). The change in sensitivity by preservation was shown by A log E.

TABLE 3.COMPOSITION OF DEVELOPER G. Sodium sulfite (anhydrous) 2.0 N-ethyl-N-(p-hydroxyethyl) para-phenylenediaminesemihydrate 4.0 Sodium carbonate (mono-hydrate) Potassium bromide 1.0 Hydroxylamine sulfate 2.4 Water to make 1 liter.

TABLE 4 Com ound (II) sensitizing dye (1) (mg. gram (mg/gram molecule molecule of Change of silver halide) silver halide) A log E in fog EXAMPLE 3 Each of a photographic emulsion (a) containing the coupler dispersion as in Example 2 and the sensitizing dye (I), a photographic emulsion (b) containing the coupler dispersion, the sensitizing dye (I) and the compound (II) and a photographic emulsion (c) containing the coupler dispersion, the sensitizing dye (I) and the compound having the following general Formula V was applied to a baryta paper followed by drying,

NH N\ NH -on=on- NH /N NH Q3 N( some some I 1- 0330.1

and thereafter, the sensitivity change of them between one directly after coating and one after preservation was measured by the same conditions as in Example 2, the results of which are shown in Table 5.

The control compound (V) as mentioned above is one of the compound (III) having a super sensitizing effect and the structure thereof is very similar to that of the compound (II) used in the present invention but the compound showed no elfect for preventing the reduction in sensitivity by preservation.

What is claimed is:

1. A photographic silver halide element comprising a support and a silver halide light-sensitive emulsion containing a sensitizing dye having the general formula:

wherein R represents a member selected from the group Class B: an alkyl group having less than six carbon atoms and an allyl group; R represents a member selected from the above-mentioned class B; R represents a member selected from the above-mentioned class A; and Y represents a non-metal atom necessary for completing a heterocyclic ring selected from the group consisting of thiazoles and benzothiazoles and a compound having the general formula:

consisting of the following class A and the following class B;

Class A:

CH2 EJH CHzO CH2) SOQH, CHzC HCHzO CH CHaCHzO (CH2)3SO3H COCH:

wherein R and R each represents a member selected from the group consisting 'of a halogen atom, a hydroxyl group, and NHR R represents a member selected from the group consisting of an aryl group and an aralkyl group; and D represents a member selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, and an amine salt.

2. The photographic silver halide element according to claim 1 wherein the proportion of saidsensitizing dye in the silver halide light-sensitive emulsion is 0.002 0.2 g. per mol of the silver halide in the emulsion.

3. The photographic silver halide element according to claim 1 wherein the proportion of said compound in the silver halide light-sensitive emulsion is'0.05-l g. per mol of the silver halide in the emulsion.

4. The photographic silver halide element according to claim 1 wherein the proportion ratio of said sensitizing dye to said compound is from 1:2 to 1:200, preferably from 1:10 to 1:60.

5. The photographic silver halide element according to claim 1 wherein said emulsion layer contains a cyan coupler.

6. The photographic silver halide element according to claim 1, wherein said sensitizing dye is O: OH

7. The photographic silver halide element according to claim 1 wherein said sensitizing dye is 3,511,664 13 14 8. The photographic silver halide element according k to claim 1 wherein said sensitizing dye is 9. The photographic silver halide element according to claim 1 wherein said sensitizing dye is 10. The photographic silver halide element according to claim 1 wherein said sensitizing dye is 11. The photographic silver halide element according to claim 1 wherein said sensitizing dye is HO N/ CH CH C S I S N H1: omonzsoan 12. The photographic silver halide element according to claim 1 wherein said sensitizing dye is H2 C H25 0 11 13. The photographic silver halide element according to claim 1 wherein said sensitizing dye is onlonomso n COCH;

N T H Hm N N H 5 H E.

N- 1. N C H m a .m

a N. v 1. Ta

0 O o s 0 MW IS IS t wk m Ur m 0 e 0 H m m m m m m m N Fm m. m H

M .0. mm w hm h mm mm Hm H H km N mr N .I XU Nr V XU mm mm 1 h H h H n 0 in O 16. The photographic silver halide element according to claim 1 wherein said compound is (II-3) N NEW l-NH- N N 01 17. The photographic silver halide element according to claim 1 wherein said compound is N NH--/ |NH-CH=CH NH V 80:11 SOaH l CH: 18. The photographic silver halide element according to claim 1 wherein said compound is (II5) References Cited UNITED'STATES PATENTS 8/1960 Jones Q 96-105 FOREIGN PATENTS 195 3' Japan.

4,724 852,074 10/1960 Great Britain.

US. Cl. X.R. 

